System and method for remediating soil and groundwater in situ

ABSTRACT

A system and method for the in-situ removal or remediation of contaminants in a soil formation containing a subsurface groundwater aquifer, the method comprising the steps of: injecting a first oxidant into the aquifer at an injection point to create a volume of influence of the first oxidant in the aquifer thereby treating the contaminants contained within the volume of influence; and injecting a compressed gas into the aquifer to increase the size of the volume of influence of the first oxidant. The injection of the compressed gas into the aquifer can also force the groundwater in the aquifer away from the injection point into a surrounding area to transport the first oxidant into the surrounding area thereby extracting contaminants from soil adjacent to the surrounding area.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of priority of U.S. ProvisionalApplication No. 60/456,085, filed on Mar. 19, 2003, the disclosure ofwhich is herein incorporated by reference in its entirety.

BACKGROUND

Groundwater, a valuable and limited natural resource, can becomecontaminated by volatile organic compounds (VOC) and semi volatileorganic compounds (SVOC) by: (i) leaking underground storage tanks andassociated piping (e.g., gasoline stations); (ii) leaking/rupturedpipelines; (iii) chemical spills along roadways, at chemical plants, ormanufacturing operations; and (iv) leaching of chemicals disposed of inlandfills.

Chemicals spilled as described above, if not immediately cleaned up, canbe absorbed into the soil, subsequently transported (depending on thesolubility of the contaminant) via rainwater to underground aquifers.Once in the aquifer, the contaminants spread and are carried downgradient. This spreading and movement of the contaminants is known as a“plume”. Drinking water wells, buildings, wetlands, etc. which are downgradient of the spill site can be negatively impacted by the contaminantplume, posing health risks to wildlife and to humans.

The treatment of contaminated soils and groundwater has gained increasedattention over the past few years because of uncontrolled hazardouswaste disposal sites. It is well documented that the most common meansof site remediation has been excavation and landfill disposal. Whilethese procedures remove contaminants, they are extremely costly and insome cases difficult if not impossible to perform.

More recently, research has focused on the conversion of contaminantscontained in soil and groundwater based on the development of on-siteand in situ treatment technologies. One such treatment has been theincineration of contaminated soils. The disadvantage of this system isin the possible formation of harmful by products includingpolychlorinated dibenzo-p-dioxins (PCDD) and polychlorinateddibenzofurans (PCDF).

In situ biological soil treatment and groundwater treatment is anothersuch system that has been reviewed in recent years. So-calledbioremediation systems, however, have limited utility for treating wastecomponents that are biorefractory or toxic to microorganisms.

Such bioremediation systems were the first to investigate the practicaland efficient injection of hydrogen peroxide into groundwater and/orsoils. These investigations revealed that the overriding issue affectingthe use of hydrogen peroxide in situ was the instability of the hydrogenperoxide downgradient from the injection point. The presence of mineralsand enzymes such as catalase and peroxidase in the subsurface catalyzedthe disproportionation of hydrogen peroxide near the injection point,with rapid evolution and loss of molecular oxygen, leading to theinvestigation of stabilizers as well as biological nutrients.

During the early biological studies from the 1980's, some investigatorsrecognized the potential for competing reactions, such as the directoxidation of the substrate by hydrogen peroxide. Certain researchersalso hypothesized that an unwanted in situ Fenton's-like reaction undernative conditions in the soil was reducing yields of oxygen through theproduction of hydroxyl radicals, a powerful oxidizing species. Such amechanism of contaminant reduction was not unexpected, sinceFenton's-type systems have been used in ex situ systems to treat soiland groundwater contamination.

Other investigators concomitantly extended the use of Fenton's-typesystems to the remediation of in situ soil systems. These studiesattempted to correlate variable parameters such as hydrogen peroxide,iron, phosphate, pH, and temperature with the efficiency of remediation.

As with bioremediation systems, in situ Fenton's systems were oftenlimited by instability of the hydrogen peroxide in situ and by the lackof spatial and temporal control in the formation of the oxidizing agent(i.e. hydroxyl radical) from the hydrogen peroxide. In particular,aggressive/violent reactions often occurred at or near the point wherethe source of the oxidizing agent (the hydrogen peroxide) and thecatalyst were injected. As a consequence, a significant amount ofreagents including the source of the oxidizing agent (hydrogen peroxide)was wasted because activity was confined to a very limited area aroundthe injection point. In addition, these in situ Fenton's systems oftenrequired the aggressive adjustment of groundwater pH to acidicconditions, which is not desirable in a minimally invasive treatmentsystem. Finally, such systems also resulted in the mineralization of thesubsurface, resulting in impermeable soil and groundwater phases due tothe deleterious effects of the reagents on the subsurface soils.

Other researchers have investigated the use of ozone, either alone or incombination with hydrogen peroxide, in ex situ advanced oxidationprocesses (AOPs) wherein ozone (O₃) and hydrogen peroxide (H₂O₂)introduced into water react with each other to form the hydroxyl radical(HO*). The hydroxyl radical formation reaction is as follows:

H₂O₂+2O₃→2OH*+3O₂  (1)

Hydrogen peroxide, ozone, and hydroxyl radical then come into contactwith and oxidize contaminants, destroying them. Glaze and Kang, J. Amer.Water Works Assoc., 80, 51 (1988), is hereby incorporated by referencein its entirety, describes an advanced oxidation process wherein ozone(O₃) and hydrogen peroxide (H₂O₂) are introduced into contaminated waterat atmospheric pressure.

Known AOP decontamination systems suffer from a number of disadvantages.A first disadvantage of known AOP decontamination systems is formationof unwanted disinfection byproducts. For example, bromide ions (Br⁻),naturally present in the water, can undergo a series of reactions toproduce bromate (BrO₃ ⁻):

3Br⁻+O₃(only)→3BrO⁻  (2)

BrO+(O₃ or HO*)→BrO₃ ⁻  (3)

Bromate has recently been designated as a suspected carcinogen, and theU.S.E.P.A. has established a maximum level for drinking water of 10μg/L. It is thus important to prevent or minimize bromate formationduring decontamination of potable water.

In reaction (2) above, neither the hydroxyl radical (HO*) nor hydrogenperoxide alone oxidize bromide to form hypobromite (BrO⁻). Moreover,reaction (3) must compete with the conversion of hypobromite back tobromide that occurs in the presence of hydrogen peroxide:

BrO⁻+H₂O₂→Br⁻  (4)

Thus when hydrogen peroxide concentration is greater, reaction (4) isfavored and the formation of bromate is discouraged. See U. von Guntenand Y. Oliveras, Envir. Sci. and Tech., 32, 63 (1998); U. von Gunten, Y.Oliveras, Wat. Res., 31, 900 (1997); W. R. Haag, and J. Hoigne, Envir.Sci. and Tech., 17, 261 (1983); U. von Gunten, J. Hoigne and A. Bruchet,Water Supply, 13, 45 which are all hereby incorporated by reference intheir entireties.

A second disadvantage of conventional ozone decontamination systems isthe limited solubility of ozone in water at atmospheric pressure. FIG. 1shows that the solubility of ozone in water increases with higherpressure. However, conventional oxidation decontamination systemsintroduce ozone at only atmospheric pressure, limiting the amount ofozone that can be dissolved in the water.

A third disadvantage is the limited concentration of ozone normallypresent in the reactant gas stream that is mixed with the water. FIG. 2shows that ozone solubility in water increases with increasing ozone inthe gas phase. Conventional oxidation systems utilize gas streamscontaining only about 1-4% ozone by weight in air, effectively limitingthe amount of ozone soluble in water.

Finally, these AOP decontamination systems suffer from a similarlimitation as all ex situ systems; namely, the necessity to pumpcontaminants from the in situ media to an external reaction vessel, arequirement which is both expensive and inefficient.

BRIEF DESCRIPTION OF THE DRAWINGS

These and other features, aspects, and advantages of the presentinvention will become better understood with regard to the followingdescription, appended claims, and accompanying drawings where:

FIG. 1 plots overall pressure versus the concentration of ozonedissolved in water, based upon a 10% (v) concentration of ozone in thegas phase for conventional oxidation decontamination;

FIG. 2 plots the concentration of ozone in the gas phase versus theresulting concentration of ozone dissolved in water for conventionaloxidation decontamination;

FIG. 3 illustrates a cross-sectional view of a representativeremediation site where an underground storage tank (UST) 10 has leakedan organic contaminant into the surrounding soils and groundwater andformed a large contaminant plume;

FIG. 4 illustrates a simplified, overhead plan view of the remediationsite shown in FIG. 3, where a UST has leaked an organic contaminant intothe surrounding soils and the extent of the resulting contaminant plumemigration is shown relative to the depth from the surface;

FIG. 5 is a cross sectional view of a typical remediation site showing aleaking UST, the resultant contaminant plume, an injector assembly, andthe general characteristics of the soils at such a site;

FIG. 6 is a detailed, cross-sectional view of one embodiment of aninjection well 65 for treating a remediation site; and

FIG. 7 illustrates one embodiment of a component diagram ofoxidant/compressed gas delivery and control system 98.

DETAILED DESCRIPTION OF THE INVENTION

In the description that follows, like parts/components are indicatedthroughout the specification and drawings with the same referencenumerals, respectively. The figures are not drawn to scale and theproportions of certain parts have been exaggerated for convenience ofillustration.

A system and method is provided for the remediation of contaminated soiland groundwater in situ by injecting oxidants and a compressed gas intoa region containing contaminated water to oxidize the contaminatespresent in the contaminated water to thereby decontaminate the region.This remediation system and process can be useful in (i) maximizingdestruction of oxidizable contaminants; (ii) minimizing costs associatedwith the consumption of expensive oxidants; and (iii) controllingquantities of bromate formed as a result of oxidation.

FIG. 3 is a representative cross-section of a typical remediation site.An underground storage tank (UST) 10 is shown discharging contaminants15 into the surrounding soils and/or groundwater creating a contaminatedregion. The discharge can impact three separate areas beneath aground-level surface 20. The discharge can contaminate soils 25, causefree floating or sinking contaminant on or beneath groundwater 30, andmay partially dissolve contaminants into the groundwater 30. As shown inFIG. 3, the soils in which the contaminant comes in contact may becomprised of several different types of soils (e.g., sand 35, silt 40,or clay 45). These different soil structures define the strata of agiven region. Frequently, these different types of soils can occur atdifferent depths from the ground-level surface 20. Additionally,representative remediation sites may include one or more undergroundstrata, formed by natural causes, which act as a natural barrier to theunconfined migration of the contaminants 15. While such strata may beimpervious to the contaminant 15 migration, if the strata remainsintact, fissures or cracks 50 that naturally occur in the strata mayprovide a conduit through which a contaminated plume 15 a may extend.The contaminant plume 15 a can include a saturated zone, a smear zone,and an unsaturated zone.

In a typical in situ remediation process, the process can begin with acharacterization of the discharged substance(s). Substances which havebeen discharged to the soil and groundwater can be chemicallycharacterized by a variety of analytical methods, most of which areknown in the art. Commonly used analytical methods for chemicalcharacterization of contaminant 15 may include conventional volatileorganic analysis (VOA) or BTEX testing, which provides a quantitativedetermination of benzene, toluene, ethyl benzene, and xylene.

Referring again to FIG. 3, a monitoring well 55 can be bored beneath theground-level surface 20 for the purpose of extracting a sample ofgroundwater 30 in an attempt to chemically characterize contaminant 15.Samples of soil 25 and/or groundwater 30 can be taken from a number oflocations throughout contaminant plume 15 a from which the nature of thedischarged substance is determined by an appropriate analytical method.In those instances where the location of the UST 10 acts as the sourceof the contaminant plume 15 a is known beforehand, a contaminant samplemay be made directly from the UST 10, if that UST 10 still contains asufficient volume of the contaminant.

Once the contaminants 15 have been defined, a three-dimensional studycan be conducted to determine the volumetric quantities of the impactedarea. The shape and size of the contaminant plume 15 a can be determinedby a number of factors: 1) the size of the UST 10 and the volume of thecontaminant that it contained at the time the leak arose; 2) the natureof the contaminant (e.g., heavy, viscous substances such as hydrocarbonbased lubricants); and 3) the geological characteristics of the soilsand water surrounding the UST 10 (e.g., loose, permeable ortightly-packed soils or fast-moving or stagnant aquifer).

Utilizing the volumetric quantities of the contaminant plume 15 a andthe composition and concentration(s) of the contaminants, an absolutequantity of contaminant to be treated can be determined. Thecalculations required for this step are generally known by those skilledin the art. A quantity of hydrogen peroxide and ozone can be empiricallydetermined for effective oxidative treatment of the contaminant mass(oxidant mass/contaminant mass is the oxidant ratio). Factors impactingthe oxidant ratio include groundwater characteristics (i.e pH,alkalinity, COD, radical scavengers, metals, etc.) The control ofbromate formation can be determined by the mole ratio of hydrogenperoxide to ozone. The mole ratio can range from between about 0.5 toabout 20. Factors impacting the mole ratio include groundwatercharacteristics (i.e. bromide concentration, pH, alkalinity, dissolvedorganic carbon (DOC), metals, etc.).

In one embodiment, the contaminant plume 15 a can be delineated byboring a number of sentinel wells 60 in an area just outside thecontaminant plume 15 a and then subsequently performing an analyticalcharacterization of samples taken from these wells. By inspection ofFIG. 4, it can be seen that the sentinel wells 60 lie outside of thecontaminant plume 15 a while the monitoring wells 55 lie within thecontainment plume 15 a. Samples taken from the monitoring wells 55 andthe sentinel wells 60 will therefore differ in composition and/orconcentration as determined through subsequent analytical testing. Afterboring a number of the monitoring wells 55 and the sentinel wells 60 andperforming an analytical characterization of samples taken from thesewells, a delineation of contaminant plume 15 a can be determined.

The delineation of the contaminant plume 15 a is not limited to just twodimensions as one may perceive from a casual inspection of FIG. 4. Forexample, a determination of the volume of the contaminant plume 15 a ismade by analyzing samples from the monitoring wells 55 and the sentinelwells 60 where the samples can be analytically characterized accordingto the sample depth in the particular well. The data produced from thisanalysis may not only characterize the distance that the contaminantplume 15 a has migrated, but also can characterize at what depth fromthe ground-level surface 20 that migration has taken place. Such acharacterization is well known in the art as vertical delineation.

Next, the hydrological and geological attributes of the contaminatedregion can be characterized to assist in the determination of the numberand position of the injection wells 65 that are required forinstallation within the contaminated region. These attributes caninclude: groundwater flow direction and gradient, groundwatercharacteristics (e.g., mineral content, alkalinity, pH, hardness, andsalinity), soil characteristics (e.g., composition of the soil, mineralcontent, alkalinity, pH, and salinity), soil transmissivity (e.g., soilporosity and soil permeability), and the profile of the geologicalstrata in the contaminated region.

Once the hydrological and geological attributes of the contaminatedregion are characterized, trials can be conducted to determine theradius of influence (ROI) of a compressed gas continuously sparged intothe contaminant plume 15 a using standard equipment known in the art.Understanding the ROI provides information useful in determining theplacement of multiple injection wells in order to effectively treat thecontaminated region. Additionally, trials can be conducted to measurethe movement of groundwater in response to pulses of compressed gas inthe contaminated plume 15 a (“dynamic response”) using standardequipment known in the art. Understanding the dynamic response (DR)permits the present remediation system and made to be optimized forpulse duration and frequency.

Based on the hydrological and geological attributes of the contaminatedregion and once the ROI and DR have been determined, a matrix ofinjection wells 65 can be mapped out in the contaminant plume 15 a suchthat there is overlap of the ROI appropriate for the contaminant plume15 a and soil conditions. The injection wells 65 may be arranged in amatrix following any arrangement or pattern depending on the shape ofthe contaminant plume 15 a. Depending on the size and characteristics ofthe contaminant plume 15 a, as little as one injection well may be usedwhile as many as 100 or more injection wells may be used for largercontaminant plumes.

One non-limiting example of a matrix of injection wells mapped out incontaminant plume 15 a is illustrated in FIG. 4. In this example, theinjection wells 65 a-f are spaced about 20 feet apart from each other ina substantially linear pattern within the contaminant plume 15 a. Themonitoring well 55 a is provided within the contaminant plume 15 a about15 feet up gradient from the substantially linear pattern of theinjection wells 65 a-f, while the monitoring well 55 b is providedwithin the contaminant plume 15 a about 35 feet down gradient from thesubstantially linear pattern of the injection wells 65 a-f. Themonitoring wells 55 a-b are capable of measuring groundwatercharacteristics (e.g., pH, dissolved oxygen, dissolved CO₂,oxidative/reductive potential (ORP), and temperature) and contaminantlevels.

FIG. 5 is a cross sectional view of a typical remediation site showing aleaking UST, the resultant contaminant plume, an injector assembly, andthe general characteristics of the soils at such a site; FIG. 6 is adetailed, cross-sectional view of one embodiment of an injection well 65for treating a remediation site. As shown in FIG. 5, each injection well65 can include at least one injector 70 to inject oxidants and acompressed gas at an injection point into the contaminant plume 15 a tooxidize and treat the contaminants. As shown in FIG. 6, the injectionwell 65 can be a bore hole 75 that extends downwardly from theground-level surface 20 of the surrounding earth and includes a bottomportion 80 that extends into or below the contaminant plume 15 a. Thebottom portion 80 of the bore hole 75 can include a highly porous medialayer 85 disposed therein to permit the oxidants and/or compressed gasexiting the injector 70 to permeate into the contaminated plume 15 a.For example, the highly porous media layer 85 may include sand, gravel,or crushed glass. Alternatively, the injection well 65 may be a screenedwell casing that extends into or below the contaminant plume 15 a. Likethe bore hole 75, the screened well casing can include a bottom portioncontaining a highly porous media layer such as sand, gravel, or crushedglass.

In one embodiment, the injector 70 can include an elongated tube 90 thatis placed within and can extend downwardly within the borehole 75. Thetube 90 can include a bottom portion 92 that can be connected to aninjection diffuser 94 and a top portion 96 that can be connected to anoxidant/compressed gas delivery and control system 98. For example, theinjection diffuser 94 may include a mesh screen, sparging tube, or otherdiffuser known in the art. As illustrated in FIG. 6, the highly porousmedia layer 85 can surround the injection diffuser 94 and fill aresulting void between the injection diffuser 94 the and bottom portion80 of the bore hole 75. The injection diffuser 94 can also prevent thehighly porous media layer 85 from occluding the tube 90 at the bottomportion 80 of the bore hole 75 thereby permitting dispersion of theoxidants and/or compressed gas throughout the contaminated plume 15 a.

To establish a liquid-tight seal around the exterior surface of tube the90 within the bore hole 75 in order to prevent fluids from flowing inand filling the bore hole 75 around the tube 90, a sealing layer 99 canbe provided above the layer of the highly porous media layer 85. In oneembodiment, the Sealing layer 99 can be formed of water-swellablebentonite material positioned within the bore hole 75 such that thebentonite material contacts the walls of the bore hole 75 and surroundsthe tube 90. The bentonite material completely fills the void betweenthe tube 90 and the bore hole 75 when the bentonite material contactswater thereby forming a seal. In this manner, the portion of theinjector 70 located below the sealing layer 99 is completely andeffectively sealed from the upper portion of the bore hole 75.

As shown, FIG. 7 illustrates one embodiment of a component diagram ofoxidant/compressed gas delivery and control system 98. As shown in FIG.7, oxidant/compressed gas delivery and control system 98 is illustratedin a component diagram where the solid lines indicate a hard connectionvia conduit, tubing, or the like and the dashed lines indicate that thecomponents are in signal communication with each other. In oneembodiment, the system 98 can include an injection panel 100 thatincludes compressed gas and oxidant manifolds and injection valves, flowmeters, and pressure gages. The system 98 can further include an ozonegenerator device 105 configured to generate ozone from oxygen and anozone delivery device 110 configured to deliver ozone to the injector 70via the injection panel 100.

In one embodiment, the oxygen may be supplied to the ozone generatordevice 105 via an oxygen generator device 115 or a supply of oxygentanks. Although it is preferable to utilize ozone generated from oxygenbecause generation of ozone in this manner results in a supply of gascontaining substantial concentrations of ozone, it is possible to useozone generated from air yielding lower concentrations of ozone. Thus,the term “ozone” as used herein can refer to an ozone/oxygen mixture andan ozone/air mixture. As shown in FIG. 2, these elevated gas phase ozoneconcentrations lead to larger quantities of ozone being dissolved in thecontaminated water flow. An additional benefit of utilizing ozonegenerated from oxygen is that oxygen is itself an oxidant. Becausecontaminated groundwater is typically devoid of oxygen, the introductionof oxygen along with ozone can replenish the oxygen content of thegroundwater and may oxidize contaminants, as well as promote biologicalelements that may further reduce contaminant levels.

In one embodiment, the ozone generator device 105 can be an ASTeX Model8403 modified to maintain a pressure in the generator higher than thatof the contaminated water flow. Generation of ozone from oxygen in thismanner can produce an ozone/oxygen mixture stream having ozoneconcentrations between about 1 and about 14% by weight in oxygen, withmost typical ozone concentrations between about 5% and about 10% byweight in oxygen.

With continued reference to FIG. 7, the system 98 can further include ahydrogen peroxide reservoir 120 and a hydrogen peroxide delivery device125 configured to deliver a hydrogen peroxide solution to the injector70 via the injection panel 100. In general, the hydrogen peroxidereservoir 120 can be commercially supplied. In one embodiment, thehydrogen peroxide solution can include hydrogen peroxide inconcentrations up to 70% by weight in water. As used herein, the term“hydrogen peroxide” can also refer to a hydrogen peroxide solution. Inanother embodiment, the hydrogen peroxide solution can include hydrogenperoxide in concentrations up to 35% by weight in water.

Furthermore, the system 98 can further include a gas compressor 130 anda gas delivery device 135 configured to deliver a compressed gas to theinjector 70 via the injection panel 100. In one embodiment, thecompressed gas can be air. Alternatively, the compressed gas may benitrogen, oxygen, or carbon dioxide. If the compressed gas is not air,then the system 98 may further include a gas source (e.g., nitrogen,oxygen, or carbon-dioxide) to supply the gas to gas compressor 130.

Optionally, the system 98 may further include acid and biologicalnutrient reservoirs (not shown) and respective delivery devices (notshown) to deliver acids such as acetic acid, phosphoric, or sulfuricacid in conjunction with hydrogen peroxide to enhance a Fenton's typereaction and to deliver biological nutrients to enhance biologicaldegradation of the organic contaminates.

To control the timing (duration and frequency) and order of delivery ofthe oxidants/compressed gas to each injector 70, a central controller140 can be provided in signal communication with the injection panel100. In one embodiment, the central controller 140 can include amicroprocessor, a programmable logic controller (PLC), analog anddigital interface modules, and customized software. The centralcontroller 140 may further include a user interface 145 for operatorcontrol and may optionally include a modem or other device to transmitand receive data from a remote location.

In one embodiment, the system 98 can be configured to deliver ozone,hydrogen peroxide, and compressed gas alone or in any combination to thecontaminant plume 15 a via the injector 70. In other words, ozone may bedelivered to the contaminant plume 15 a via the injector 70 alone or incombination with compressed air and hydrogen peroxide. Likewise,compressed gas may be delivered to the contaminant plume 15 a via theinjector 70 alone in combination with ozone and hydrogen peroxide.Similarly, hydrogen peroxide can be delivered to the contaminant plume15 a via the injector 70 alone or in combination with ozone andcompressed gas. Although a single injection point may be used, it willbe appreciated that more than one injection point can be used to deliverthe oxidants and compressed gas. For example, multiple injectors can beused to separately deliver the ozone, hydrogen peroxide, and compressedgas to the contaminant plume 15 a.

Examples of possible injection combinations of ozone, hydrogen peroxide,compressed gas, and a combination of ozone/compressed gas that can bedelivered to the contaminant plume 15 a via the injector 70 (hereinafterreferred to as “injection sequences”) are illustrated in Table I. Forexample, as shown in injection sequence number 1, hydrogen peroxide (ata particular concentration, pressure, and flow rate) can be firstinjected into the contaminant plume 15 a for 10 minutes, creating asphere of influence of the hydrogen peroxide followed by an injection ofcompressed gas (at a particular concentration, pressure, and flow rate)for 10 minutes to increase the size of the sphere of influence of thehydrogen peroxide, followed by a status quo period (indicated as nothingin Table I) for 10 minutes, and followed by an injection of ozone andcompressed air combined (at a particular concentration, pressure, andflow rate) for five minutes. As used herein, although the term “sphereof influence” has meaning to one skilled in the art, the term “volume ofinfluence” can also be used to represent the fact that the injectedhydrogen peroxide or any other oxidant does not create a perfect sphereshape. Although only four injection sequences are illustrated in TableI, it is understood that there are numerous possible injectioncombinations that may be employed.

TABLE I Sequence No. Injection 1 Injection 2 Injection 3 Injection 4 1hydrogen compressed gas nothing ozone/compressed peroxide (10 minutes)(10 minutes) gas combined (10 minutes) (5 minutes) 2 hydrogen compressedgas ozone nothing peroxide(10 (10 minutes) (5 minutes) (10 minutes)minutes) 3 hydrogen ozone/compressed nothing compressed gas peroxide gascombined (10 minutes) (5 minutes) (10 minutes) (5 minutes) 4 hydrogennothing ozone/compressed compressed gas peroxide (10 minutes) gascombined minutes) (5 minutes) (5 minutes)

Furthermore, the system 98 can be configured to deliver the same ordifferent injection sequences at different injection wells 65 situatedin the contaminant plume 15 a. For example, while the injector ininjector well 65 a is performing injection sequence 1 illustrated above,the injector in injector well 2 can be performing the same injectionsequence 1 or can be performing other injection sequences (e.g.,injection sequence 2-4 or other sequences).

As stated above, the central controller 140 can be configured to controlthe amount, pressure, flow rate, and concentration (in the case ofozone) of the oxidants and compressed gas delivered to contaminant plumevia injector 70. The allocation (or amount) of the oxidants delivered toeach injection well 65 can be determined based on the characteristics ofthe contaminant plume 15 a. The allocation of compressed gas to eachinjection well 65 can be determined based on the oxidant allocation andDR. The time constants for the injection sequences, injection pulsationfrequencies, and magnitude (i.e., pressure and/or flow rate) can then beempirically determined and programmed into the user interface 145 of thecentral controller 140.

Once all of the injection parameters for the oxidants and compressed gas(e.g., timing (i.e., duration and frequency), amount, pressure, flowrate, oxidant ratio, and mole ratio) have been determined and storedinto the central controller 140, a user can then program the injectionsequences for each injection well 65 as shown above in Table I. At thistime, the remediation system can then be operated to inject the oxidantsand compressed gas into the contaminant plume 15 a according to theprogrammed injection sequences. The injection sequences includeinjecting the oxidants and other chemicals into a well or series ofwells and forcing the migration of the oxidants into the contaminatedarea by pulsed injections of compressed gas.

In one embodiment, the injection of compressed gas following theinjection of one or more oxidants can increase the sphere or volume ofinfluence of the oxidant(s) in the aquifer. By increasing the sphere ofinfluence of the oxidant(s) in the aquifer, the oxidant(s) can destroymore contaminants present in the groundwater or saturated zone of thecontaminant plume 15 a.

In another embodiment, the injection of compressed gas can also forcethe contaminated groundwater away from the injection well or injectionpoint into a surrounding area (e.g., the saturated, smear, orunsaturated zones of the contaminate plume 15 a) and transport theoxidants and other chemicals into the area surrounding the injectionwell(s). When the groundwater is forced into the surrounding area, thegroundwater can extract or desorb contaminants from soil adjacent to thesurrounding area. When the injection of the compressed gas isdiscontinued, the groundwater can return to an over adjacent to thewell(s) thereby returning the contaminants extracted from the soil tothe area adjacent to the injection well(s).

In one embodiment, the flow and pressure of compressed gas and theperiodic cycling of injections can be regulated to optimize thetransport of the oxidants into the contaminated area surrounding theinjection well(s). The pulsed injection of compressed gas can act toagitate the soil/groundwater matrix and desorb organic contaminants fromthe soil thereby bringing them into solution by forced turbulence in thecontaminant plume 15 a. The movement of water or the displacement ofwater can help to mix the oxidants to produce more hydroxyl radicals.

Because the remediation system described herein can inject a gas (i.e.,ozone, compressed air, or combination of both) and a liquid (i.e.,hydrogen peroxide) through the same injector, the gas and liquid canreadily and intimately mix in the soil in the correct proportions,facilitating the desirable hydroxyl radical reaction. Of course, manyother combinations of liquids including a variety of dissolved gases,chemicals such as acids, and/or biological agents such as biologicalnutrients can also be employed. Examples of acids that could be injectedinclude acetic acid, phosphoric, or sulfuric acid. The injection of anacid in conjunction with hydrogen peroxide can enhance a Fenton'sreaction. Examples of biological nutrients that can be utilized includeammonium phosphate or propane. The injection of a biological nutrientcan also enhance the biological degradation of the organic contaminates.If air or another gas is also injected into the soil, it can help tocause microfractures, facilitating dispersion of the liquids and, if airor other oxygen-containing gas is used, can also supply oxygen forbiological agents.

During operation of the remediation system described herein, real-timemeasurements of dissolved oxygen (DO), oxidation/reduction potential(ORP), and temperature at monitoring wells 55 a, 55 b may be taken tore-allocate the injection of hydrogen peroxide and ozone-containing gasin each of injection wells 65 a-65 f so as to maintain constant, optimumlevels of DO, ORP, and temperature. Furthermore, real-time measurementsof dissolved CO₂ at monitoring wells 55 a, 55 b may be taken tore-allocate the injection of hydrogen peroxide and ozone-containing gasin the event that CO₂ declines significantly, indicating a reduction incontaminants. Optionally, the re-allocation of ozone-containing gas maybe accomplished by the reduction of the ozone concentration in the ozonecontaining gas.

The invention can be illustrated further by the following examples,which are not to be construed as limiting its scope.

EXAMPLE 1

Utilizing a single injection well to deliver oxidants and compressed airto a contaminated region containing contaminated groundwater, thefollowing injection sequence is used.

Step Duration H₂O₂ Ozone Air 1 10 min yes no no 2 10 min no no yes 3 20min no no no 4 10 min no yes yes 5 10 min no no no

As shown above, H₂O₂ can be first injected into the contaminated regionfor 10 minutes to form a pool of H₂O₂ into the immediate area of theinjection point (i.e., sphere of influence). Compressed air can then beinjected into the contaminated region for 10 minutes to mix the H₂O₂with the groundwater and agitate the contaminants to bring them intosolution. The addition of the compressed air can also serve to de-waterthe area around the injection point. Following the injection of thecompressed air for 10 minutes, no action is taken for 20 minutes toallow the de-watered area to collapse such that the H₂O₂ and groundwaterthat were driven out of the area around the injection point will returnto the area thereby further mixing and agitating the area. Diluted ozonecan then be injected into the H₂O₂ and groundwater solution for 10minutes thereby creating OH* radicals, which will oxidize the aqueouscontaminants and will also further agitate the soil and groundwater.Following the injection of ozone for 10 minutes, no action can be takenfor 10 minutes to allow the groundwater to collapse again. This fivestep injection sequence may be repeated until the contaminated region isremediated.

EXAMPLE 2

Utilizing multiple injection wells to deliver oxidants and compressedair to a contaminated region containing contaminated groundwater wherethe injection wells were positioned as shown in FIG. 4 so that the ROIoverlap and where a highly contaminated region existed between injectionwells 65 b and 65 c, the following injection sequence was used.

Step Duration H₂O₂ Ozone Air 1 10 min yes (well 65b) no no 2 10 min nono yes (well 65a) 3 10 min no yes (well 65c) yes (well 65c)As shown above, H₂O₂ was first injected into the contaminated region for10 minutes to form a pool of H₂O₂ (i.e., sphere of influence) into theimmediate area of the well 65 b, which is the center of the three wells(65 a-c). Compressed air was then injected into the well 65 a for 10minutes to push the groundwater closer to well 65 a, mix the H₂O₂ withthe groundwater closer to the well 65 b, and agitate the contaminants tobring them into solution. Following the injection of compressed air for10 minutes, diluted ozone and compressed air was then injected into thewell 65 c for 10 minutes thereby creating OH radicals, which willoxidize the aqueous contaminants closer to the well 65 b because of theROI overlap. This three step injection sequence was repeated until thecontaminated region was remediated.

The remediation process described above utilizing the above injectionsequence yielded the following results where MTBE represents Methyltert-Butyl Ether, TBA represents tert-Butyl Alcohol, TAME representstert-Amyl Methyl Ether, and ND represents non-detectable. The first datapoint is from monitoring well 55 a, which is about 15 feet up gradientof the linear array of injection wells 65 a-f.

Contaminant Levels (ppb) Time MTBE TBA TAME prior to 1500 790 750remediation 9 wks into ND ND ND remediation (<0.5) (<10) (<0.8)The second data point is from monitoring well 55 b, which is about 35feet down gradient of the linear array of injection wells 65 a-f.

Contaminant Levels (ppb) Time MTBE TBA TAME prior to 440 34 3remediation 9 wks into ND ND ND remediation (<0.5) (<10) (<0.8)

EXAMPLE 3

A release of unleaded gasoline was identified at a site during regulatedunderground storage tank (UST) upgrade activities during September 1995.Soil sample analytical results indicated that benzene, toluene,ethylbenzene and xylenes (BTEX) exceeded applicable PennsylvaniaDepartment of Environmental Protection (PADEP) soil quality standards.

Soil borings were completed using direct-push and hollow-stem augerdrilling methods during October and November 1995. The findings of theseinvestigations confirmed the presence of benzene and toluene in soil atconcentrations exceeding applicable PADEP soil quality standards northand northwest of the dispenser island area and product piping.

In November 1995, three monitoring wells (MW-1, MW-2, and MW-3) wereinstalled. Five additional monitoring wells (MW-4 through MW-8) wereinstalled in 1998. A groundwater pump and treat system began operationin April 1999 and is currently operating. Since groundwater monitoringwas initiated onsite in December 1995, dissolved benzene and methyl tertbutyl ether (MTBE) have been detected at MW-2, MW-3, and MW-3 ingroundwater above applicable PADEP media specific concentrations (MSCs).Dissolved MTBE has also been detected offsite to the north and northeastof the site above the MSC.

During April, 2003, additional soil quality delineation was completed onthe rear portion of the site. The findings confirmed that benzene,toluene, ethylbenzene, MTBE and naphthalene were detected atconcentrations above applicable PADEP MSCs in several borings along thenorth and northeast property boundary.

The available drill logs also indicate that groundwater was encounteredat depths ranging from 12 to 15 feet below grade, slightly above thebedrock surface. Static water levels measured at site monitoring wellson Apr. 17, 2003 range from three to nine feet below grade. It appearsthat the aquifer at the site comprises a shallow water-bearing zoneperched above the bedrock surface and a deeper water-bearing zoneoccurring in fractures and bedding planes of the underlying bedrock.

The two injection wells were constructed using 304 stainless steelriser. Each of the injection wells was constructed by installing two½-inch diameter stainless steel points (one point for oxygen/ozone andone point for hydrogen peroxide) into a six-inch diameter borehole. Eachborehole was advanced to an appropriate depth below the static watertable (maximum of 20 feet bgs). Each hydrogen peroxide injection wellwas completed with a two foot section of stainless steel well screen.Each oxygen/ozone injection well was completed with a ceramic diffuserat the end of the riser. The ozone diffuser was installed at the bottomof the boring. Sandpack was placed surrounding the diffuser and to adepth of two feet above the top of the diffuser. A bentonite seal(minimum of one foot thick) was placed above the sandpack surroundingthe ozone diffuser to prevent short-circuiting. Following theinstallation of both the diffuser and the well screen, each borehole wasfilled with concrete grout and completed with a protective, lockingaccess vault, which was mounted flush to grade.

Of the two injection points, the first injection point (IP-1) wasinstalled in the existing groundwater interception trench and isintended to address hydrocarbon impact to groundwater above bedrock,observed at approximately 14 feet bgs. The second injection point (IP-2)was installed into the top of the bedrock surface, observed at 14 to 16feet bgs.

Observation wells were located within 15 feet of the injection pointsand were constructed with two-inch diameter schedule 40 PVC screen andcasing. Clean silica sand filter pack was installed across the screenedinterval and a bentonite seal was installed above the sand pack toprevent the migration of surface water or groundwater from zones abovethe screened interval into the well. The remaining annular space abovethe bentonite seal was filled with grout to surface grade.

Feasibility testing was conducted on Jun. 27, 2003 utilizing AStechnology and on Jul. 2, 2003 utilizing the chemical oxidationtechnology at two locations (IP-1 and IP-2). AS was utilized to estimatethe oxygen/ozone radius-of-influence under varying air injection flowrates. Air injection can be effectively used to estimate the expectedradius-of-influence during ozone injection since both air andoxygen/ozone will be distributed similarly in the subsurface undervarying injection flow rates (typically between 1 and 10 standard cubicfeet per minute [scfm]). AS feasibility testing was performed using DataAcquisition and Processing Laboratory (DAPL). which is a self-containedplatform that provides computerized on-site real-time data acquisitionand processing evaluation.

On Jul. 2, 2003, a one-day oxygen, ozone, air, and hydrogen peroxideinjection test was conducted at the site. The oxygen/ozone stream usedwas a mixture of at least 90% oxygen and a maximum of 10% ozone at aflow rate of up to 0.7 scfm. This flow rate could have been increased upto 20 scfm by adding supplemental atmospheric air pumped into thesubsurface via oil-less air compressors. Approximately 110 gallons ofhydrogen peroxide were injected into the two injection points during thechemical oxidation event.

The ozone components of the system include an air compressor, pressureswing adsorption unit, and ozone generator. The air compressor andpressure swing adsorption unit are utilized to generate oxygen and arecommonly used with oxygen/ozone generators. The air produced by thecompressor is directed into a pressure swing adsorption unit whichadsorbs the nitrogen naturally present in the air stream, resulting inan oxygen-rich air stream to feed the ozone generator. The nitrogenadsorption unit periodically exhausts small volumes of nitrogen backinto the atmosphere. The flow of the oxygen stream is monitored by aflow indicator. The flow is also transmitted to a flow controller whichoperates a solenoid valve to ensure a constant flow is delivered to theozone generator.

Testing was conducted in the existing interception trench at injectionpoint IP-1 and in the native soil at injection point IP-2 to obtain thenecessary information to determine the feasibility of the technology andto provide the necessary data for the subsequent installation of aremediation system for the site.

Chemical oxidation testing was performed at injection points IP-1 andIP-2 to determine the effectiveness and applicability of the technologyto site conditions. Testing was completed at each injection point inseveral steps ranging from low flow, high ozone concentration to highflow, low ozone concentration. The moderate to high flow steps wereachieved by adding compressed air to the oxygen/ozone stream as acarrier gas. Prior to injection of the ozone/oxygen stream,approximately 50 gallons of 18% hydrogen peroxide was injected into eachinjection well to saturate the subsurface with peroxide. Subsequentinjections of the oxygen/ozone stream allows for the production ofhydroxyl radicals, which are more powerful oxidizers than ozone orhydrogen peroxide individually, through the reaction of ozone andhydrogen peroxide. Similar to the AS testing, groundwater qualitymeasurements were obtained throughout testing. In addition, headspacereadings were collected for LEL, percent oxygen, and ozone.

An evaluation of the groundwater results indicates an overall reductionin the BTEX and MTBE concentrations as summarized in Table 2. The mostsignificant reduction was observed, as expected, at injection well IP-2.The initial BTEX and MTBE concentrations were 293.7 micrograms per liter(μg/L) and 164 μg/L, respectively. Following all testing activities, theBTEX and MTBE concentrations were reduced to non-detect (ND) at areporting limit of 1 μg/L.

Reductions in dissolved BTEX concentrations at the three newly installedobservation wells were 10%, 14%, and 11% for monitoring wells MW-9,MW-10, and MW-11, respectively, between the post AS samples and finalsamples. Dissolved MTBE concentrations were reduced by 26%, 29%, and 9%at wells MW-9, MW-10, and MW-11, respectively. The overall reductionsobserved at monitoring well MW-9, comparing pre-testing and finalsamples were 20% for BTEX and 47% for MTBE. Monitoring wells MW-10 andMW-11 are located immediately downgradient of the two injection points.Monitoring well MW-9 is located immediately upgradient of the twoinjection points. The results from the other three observation wells(MW-3R, SP-East, and SP-West), located side-gradient to the injectionarea, did not show decreases in concentrations. All three of themonitoring wells which indicated dissolved BTEX and MTBE concentrationdecreases (MW-9, MW-10, and MW-11) measured positive pressure influencesduring chemical oxidation testing at IP-1 and IP-2.

TABLE 2 FEASIBILITY TEST GROUND WATER ANALYTICAL RESULTS - VOCs WellEthyl- BTEX % MTBE % ID Description Benzene Toluene benzene Xylenes BTEXMTBE Difference Difference IP-1 Pre-Rem 212.0 19.0 140.0 329 700.0 177 —— Post-Rem NA NA NA NA — NA — — IP-2 Pre-Rem 26.2 15.7 55.8 196 293.7164 — — Post-Rem ND (1) ND (1) ND (1) ND (1) — ND (1) 100%  100%  MW-3RPost-Air 49.6 1.6 83.8 13.5 148.5 137 — — Post-Rem 55.1 1.7 114.0 19.5190.3 120 −28%  12% MW-9 Pre-Rem 394.0 10.4 125.0 68.6 598.0 3,210 — —Post-Air 354.0 9.0 105.0 65.8 533.8 2,370 11% 26% Post-Rem 296.0 9.5105.0 69.9 480.4 1,690 20% 47% MW-10 Post-Air 23.2 0.57 16.6 3.9 44.3287 — — Post-Rem 23.4 ND (1) 9.8 4.9 38.1 240 14% 16% MW-11 Post-Air1,470 602 988 4,570 7,630 7,940 — — Post-Rem 1,360 584 1,100 3,740 6,7847,220 — — SP-East Post-Air 80.7 27.7 16.1 289.0 413.5 245 — — Post-Rem102.0 36.9 13.3 277.0 429.2 449 −4% −83%  SP-West Post-Air 57.8 6.3 16.394.2 174.6 168 — — Post-Rem 45.6 4.5 13.2 80.3 143.6 178 18% −6% Notes:VOCs—volatile organic compounds Pre-Rem = Pre-Remediation Post-Rem =Post-Remediation Post-Air = Post-Air Sparge ND = Not Detected NA = Notanalyzed MTBE = Methyl tert-butyl ether BTEX = sum of benzene, toluene,ethylbenzene, and total xylenes All values are reported in microgramsper liter (μg/L)

Although the invention has been described with reference to thepreferred embodiments, it will be apparent to one skilled in the artthat variations and modifications are contemplated within the spirit andscope of the invention. The drawings and description of the preferredembodiments are made by way of example rather than to limit the scope ofthe invention, and it is intended to cover within the spirit and scopeof the invention all such changes and modifications.

1. A method for the in-situ removal or remediation of contaminants in asoil formation containing a subsurface groundwater aquifer, the methodcomprising the steps of: injecting a first oxidant into the aquifer atan injection point to create a volume of influence of the first oxidantin the aquifer thereby treating the contaminants contained within thevolume of influence; and injecting a compressed gas into the aquifer toincrease the size of the volume of influence of the first oxidant. 2.The method of claim 1, wherein the injection of the compressed gas intothe aquifer also forces the groundwater in the aquifer away from theinjection point into a surrounding area thereby transporting the firstoxidant into the surrounding area.
 3. The method of claim 2, wherein thesurrounding area includes the saturated zone.
 4. The method of claim 2,wherein the surrounding area includes the smear zone.
 5. The method ofclaim 3, wherein the injection of the compressed gas into the aquiferforces the groundwater into the surrounding area thereby extractingcontaminants from soil adjacent to the surrounding area.
 6. The methodof claim 5, further comprising the step of: after the compressed gasinjection step, allowing the groundwater to return to the volume ofinfluence of the first oxidant from the surrounding area bydiscontinuing injection of the compressed gas, thereby returning thecontaminants extracted from the soil to the volume of influence of thefirst oxidant.
 7. The method of claim 1, wherein the first oxidant isselected from the group consisting of a hydrogen peroxide solution, anozone/air mixture, an ozone/oxygen mixture, and combinations thereof. 8.The method of claim 1, further comprising the step of: injecting asecond oxidant into the aquifer to treat the contaminants containedwithin the aquifer.
 9. The method of claim 8, wherein the first oxidantis a hydrogen peroxide solution and the second oxidant is anozone/oxygen mixture.
 10. The method of claim 8, wherein theconcentration of hydrogen peroxide in the hydrogen peroxide solution isless than about 70% by weight in water.
 11. The method of claim 8,wherein the first and second oxidants chemically react with each otherto form hydroxyl radicals.
 12. The method of claim 1, further comprisingthe step of: injecting a second oxidant in combination with compressedgas into the aquifer to treat the contaminants contained within theaquifer.
 13. The method of claim 1, wherein the injection of thecompressed gas into the aquifer occurs after the conclusion of theinjection of the oxidant into the aquifer.
 14. The method of claim 1,wherein the compressed gas is selected from the group consisting of air,nitrogen, oxygen, carbon dioxide, and any combination thereof.
 15. Themethod of claim 1, wherein the injection of the compressed gas isperiodically cycled.
 16. A method for the in-situ removal or remediationof contaminants in a soil formation containing a subsurface groundwateraquifer, wherein the contaminants are spread out by diffusion, movementof the groundwater, and other mechanisms to form a contaminant plume,the method comprising the steps of: alternately injecting, in any order,a hydrogen peroxide solution, an ozone/oxygen mixture, and compressedgas into the aquifer at an injection point to treat the contaminantscontained within the groundwater, wherein the injection of thecompressed gas forces the groundwater away from the injection point intoa saturated zone or smear zone of the contaminant plume therebytransporting the hydrogen peroxide solution and the ozone/oxygen mixtureinto the saturated zone or smear zone of the contaminant plume.
 17. Themethod of claim 16, wherein the groundwater transported into thesaturated zone or smear zone of the contaminant plume desorbscontaminants from soil adjacent to the saturated zone or smear zone ofthe contaminant plume thereby bringing such contaminants into solutionto be subsequently treated.
 18. The method of claim 17, furthercomprising the step of: after the compressed gas injection step,allowing the groundwater to return to the injection point from thesaturated zone or smear zone of the contaminant plume thereby returningthe contaminants desorbed from the soil to an area adjacent to theinjection point.
 19. The method of claim 18, wherein the injection ofthe compressed gas is periodically cycled to agitate the contaminants tobring them into solution with the groundwater.
 20. The method of claim17, wherein a second oxidant in combination with the compressed gas canbe alternately injected into the aquifer to treat the contaminantscontained within the aquifer.
 21. The method of claim 17, furthercomprising the step of: alternately injecting, in any order, one or moreoxidants and compressed gas into the aquifer at multiple injectionpoints to optimize the direction and movement of the oxidants within thecontaminant plume.
 22. The method of claim 21, wherein the alternatinginjection of one or more oxidants and compressed gas into the aquifer atmultiple injection points increases the desorption and agitation of thecontaminants into the groundwater.
 23. A method for the in-situ removalor remediation of contaminants in a soil formation containing asubsurface groundwater aquifer, the method comprising the steps of:intermittently introducing, individually and in any order, a firstoxidant, a second oxidant, and compressed gas into the groundwater totreat the contaminants contained within the aquifer, wherein theintroduction of each oxidant creates a volume of influence of eachoxidant, wherein the introduction of the compressed gas increases thesize of each volume of influence of each oxidant.
 24. The method ofclaim 23, wherein a second oxidant in combination with the compressedgas can be alternately injected into the aquifer to treat thecontaminants contained within the aquifer.